U.S. patent application number 10/733086 was filed with the patent office on 2005-06-16 for synthesis of bis(azinyl)amine-bf2 complex.
This patent application is currently assigned to Eastman Kodak Company. Invention is credited to Owczarczyk, Zbyslaw R..
Application Number | 20050131234 10/733086 |
Document ID | / |
Family ID | 34620612 |
Filed Date | 2005-06-16 |
United States Patent
Application |
20050131234 |
Kind Code |
A1 |
Owczarczyk, Zbyslaw R. |
June 16, 2005 |
SYNTHESIS OF BIS(AZINYL)AMINE-BF2 COMPLEX
Abstract
Disclosed is a process of forming a bis(azinyl)amine-BF.sub.2
complex, where a boron atom is complexed by two ring nitrogens of a
deprotonated bis(azinyl)amine compound, comprising the step of
reacting BF.sub.3 with a protonated bis(azinyl) amine in the
presence of a polar aprotic organic solvent that is not reactive
with the BF.sub.3 under reaction conditions. Such process provides
good yields, even when a bulky group is present on the
bis(azinyl)amine compound.
Inventors: |
Owczarczyk, Zbyslaw R.;
(Webster, NY) |
Correspondence
Address: |
Paul A. Leipold
Patent Legal Staff
Eastman Kodak Company
343 State Street
Rochester
NY
14650-2201
US
|
Assignee: |
Eastman Kodak Company
|
Family ID: |
34620612 |
Appl. No.: |
10/733086 |
Filed: |
December 11, 2003 |
Current U.S.
Class: |
546/13 |
Current CPC
Class: |
C07F 5/022 20130101 |
Class at
Publication: |
546/013 |
International
Class: |
C07F 005/02 |
Claims
1. A process of forming a 2-2' bis(pyridyl amine-BF.sub.2 complex,
where a boron atom is complexed by two ring nitrogens, comprising
the step of reacting BF.sub.3 with an amine having Formula (1)
8wherein: A and A' represent independent azine ring systems
corresponding to 6-membered aromatic ring systems containing at
least one nitrogen; each X.sup.a and X.sup.b is an independently
selected substituent, two of which may join to form a fused ring to
A or A'; m and n are independently 0 to 4; and atoms 1, 2, 3, 4,
1', 2', 3', and 4' are carbon atoms; in the presence of a polar
aprotic organic solvent containing a nitrile group that is not
reactive with the BF.sub.3 under reaction conditions and has the
Formula: 9wherein R.sub.1, R.sub.2 and R.sub.3 each independently
represents hydrogen, fluorine, alkyl, aryl, alkoxy, aryloxy,
dialkylamino, diarylamino, cyano, or nitro groups wherein at least
one of R.sub.1, R.sub.2 and R.sub.3 is not H; and R.sub.1 and
R.sub.2, R.sub.2 and R.sub.3 or R.sub.1 and R.sub.3 may join to
form a cycloalkyl or an aryl ring group.
2-4. (canceled)
5. The process of claim 1 wherein at least two of R.sub.1, R.sub.2
and R.sub.3 are not H.
6. The process of claim 1 wherein R.sub.1 and R.sub.2 represent H
and R.sub.3 represents a methyl group.
7. The process of claim 1 wherein R.sub.1 and R.sub.2 represent H
and R.sub.3 represents an ethyl group.
8. The process of claim 1 wherein at least two of R.sub.1, R.sub.2
and R.sub.3 are H.
9. The process of claim 1 wherein the BF.sub.3 source is selected
from the group consisting of BF.sub.3 gas, BF.sub.3 solution in an
organic solvent or BF.sub.3 complex with organic solvent or
compound.
10. The process of claim 1 wherein the BF.sub.3 source is selected
from the group consisting of BF.sub.3 complexed with diethyl ether,
dimethyl ether or tetrahydrofuran.
11. The process of claim 1 wherein BF.sub.3 is used in the amount
1-50 equivalents per mol of the amine compound having Formula
(1).
12. The process of claim 1 wherein the reaction is performed at a
temperature of at least 18.degree. C.
13. The process of claim 1 wherein the reaction is performed at a
temperature of at least 80.degree. C.
14. The process of claim 1 wherein the reaction is performed at a
temperature of at least 115.degree. C.
15. (canceled)
16. The process of claim 1 where at least one X.sup.a or X.sup.b is
present containing 4 or more carbon atoms.
17. The process of claim 16 wherein the X.sup.a or X.sup.b group is
selected from the group consisting of phenyl and t-butyl
groups.
18. The process of claim 17 wherein the X.sup.a or X.sup.b group is
a phenyl group.
19. The process of claim 17 wherein the X.sup.a or X.sup.b group is
a phenyl group containing at least one methyl group
substituent.
20. The process of claim 17 wherein the X.sup.a or X.sup.b group is
a mesityl group.
21. The process of claim 1 wherein the amine-BF.sub.2 complex is
selected from the following: 101112
Description
FIELD OF THE INVENTION
[0001] This invention relates to the field of organic synthesis and
to a process of forming a bis(azinyl)amine-BF.sub.2 complex, where
the boron atom is complexed by two ring nitrogens of a deprotonated
bis(azinyl)amine compound, comprising reacting BF.sub.3 with a
protonated bis(azinyl)amine compound in the presence of polar
aprotic organic solvent that is not reactive with the BF.sub.3
under reaction conditions.
BACKGROUND OF THE INVENTION
[0002] Electroluminescent devices are well-known for their utility
in providing light emissions. Among the emitting materials useful
in such devices are bis(azinyl)amine-BF.sub.2 complex, where the
boron atom is complexed by two ring nitrogens of a deprotonated
bis(azinyl)amine compound. Pending and commonly assigned U.S. Ser.
No. 10/183,242, filed Jun. 27, 2002 CIP of U.S. Ser. No 10/086,085
filed Feb. 28, 2002 teaches a method of preparing
bis(azinyl)amine-BF.sub.2 complexes by reacting BF.sub.3 with a
protonated bis(azinyl)amine compound in toluene as an organic
solvent. Sathyamoorthi et al. (Heteroatom Chemistry 1993, 6, 603 )
describes the synthesis bis(azinyl)amine-BF.sub.2 complex using
toluene and dichloromethane as an organic solvent. While these
methods produced the desired product generally in satisfactory
yield, they gave low yield, typically below 5%, when the selected
deprotonated bis(azinyl)amine compound was substituted with bulky
groups such as phenyl, t-butyl or mesityl groups.
[0003] It is a problem to be solved to provide an efficient process
for the synthesis of bis(azinyl)amine-BF.sub.2 complexes,
especially those with bulky substituents.
SUMMARY OF THE INVENTION
[0004] The invention provides a process of forming a
bis(azinyl)amine-BF.sub.2 complex, where a boron atom is complexed
by two ring nitrogens of a deprotonated bis(azinyl)amine compound,
comprising the step of reacting BF.sub.3 with a protonated
bis(azinyl) amine in the presence of a polar aprotic organic
solvent that is not reactive with the BF.sub.3 under reaction
conditions.
[0005] Such process provides good yields, even when a bulky group
is present on the bis(azinyl)amine compound.
DETAILED DESCRIPTION OF THE INVENTION
[0006] The detailed invention is summarized above. The process
enables synthesis of bis(azinyl)amine-BF.sub.2 complexes by
reacting a protonated bis(azinyl)amine compound with BF.sub.3 or a
BF.sub.3 source in high yield. The phrase protonated means that at
least one nitrogen atom of the compound is substituted with a
hydrogen atom.
[0007] The protonated bis(azinyl)amine reactant compound may be
usefully represented by Formula (1): 1
[0008] wherein
[0009] A and A' represent independent azine ring systems
corresponding to 6-membered aromatic ring systems containing at
least one nitrogen;
[0010] each X.sup.a and X.sup.b is an independently selected
substituent, two of which may join to form a fused ring to A or A',
and m and n are independently 0 to 4; and
[0011] atoms 1, 2, 3, 4, 1', 2', 3', and 4' are independently
selected as either carbon or nitrogen atoms.
[0012] The compound represented by Formula 1 is reacted with either
BF.sub.3 or BF.sub.3 source, for example Et.sub.2O--BF.sub.3. Other
BF.sub.3 sources include but are not limited to
Me.sub.2O--BF.sub.3, THF--BF.sub.3, Me.sub.2S--BF.sub.3. The amount
of BF.sub.3 used in this process, relative to the starting material
as per formula (1), can range from 1-50 equivalents.
[0013] The resulting product of this process is depicted by Formula
(2): 2
[0014] wherein the substituents and variables are as described for
Formula (1).
[0015] The reaction is carried out in the presence of a polar
aprotic solvent that is not reactive with BF.sub.3 under the
reaction conditions. Conveniently it is a polar aprotic organic
solvent containing a nitrile group is conveniently one represented
by formula (3) 3
[0016] wherein:
[0017] R.sub.1, R.sub.2 and R.sub.3 each independently represents
hydrogen, fluorine, alkyl, aryl, alkoxy, aryloxy, dialkylamino,
diarylamino, cyano, or nitro groups; and R.sub.1 and R.sub.2,
R.sub.2 and R.sub.3 or R.sub.1 and R.sub.3 may join to form a
cycloalyl or an aryl ring group.
[0018] Typical substituents include alkyl, aryl alkoxy, aryloxy,
dialkylamino, diarylamino, cyano, or nitro groups. The various
alkyl groups, such as perfluoroalkyl groups, typically contain 1 to
6 carbon atoms, but less than 12 carbon atoms. The cycloalkyl
moieties usually contain from 3 to 10 carbon atoms, but typically
contain five or six carbon atoms--e.g., cyclopentyl or cyclohexyl
structure. The aryl groups are usually phenyl moieties.
[0019] The process of the invention is exemplified in the following
scheme, to prepare Inv-7: 4
[0020] Illustrative examples of boron compounds complexed by two
ring nitrogens of a deprotonated bis(azinyl)amine compound that can
be prepared using the present invention are the following: 567
[0021] Under the reaction conditions stated above, the temperature
needed to effect the formation of the complex depicted in formula
(2), is typically room temperature (18.degree. C.) to 200.degree.
C. Conveniently the reaction is carried out at temperature of at
least 80.degree. C. The temperature requirements can be also
dictated by the nature of the substituents described in Formulas
(1) and (2) and the solubility of the starting ligand (1).
[0022] Unless otherwise specifically stated, use of the term
"substituted" or "substituent" means any group or atom other than
hydrogen. Additionally, when the term "group" is used, it means
that when a substituent group contains a substitutable hydrogen, it
is also intended to encompass not only the substituent's
unsubstituted form, but also its form further substituted with any
substituent group or groups as herein mentioned. Suitably, a
substituent group may be halogen or may be bonded to the remainder
of the molecule by an atom of carbon, silicon, oxygen, nitrogen,
phosphorous, sulfur, selenium, or boron. The substituent may be,
for example, halogen, such as chloro, bromo or fluoro; nitro;
hydroxyl; cyano; carboxyl; or groups which may be further
substituted, such as alkyl, including straight or branched chain or
cyclic alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl,
cyclohexyl, 3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl;
alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy,
ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy,
2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di-t-pentylphenoxy)ethoxy,
and 2-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl,
2,4,6-trimethylphenyl, naphthyl; aryloxy, such as phenoxy,
2-methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy;
carbonamido, such as acetamido, benzamido, butyramido,
tetradecanamido, alpha-(2,4-di-t-pentylphenoxy)acetamido,
alpha-(2,4-di-t-pentylphenoxy)bu- tyramido,
alpha-(3-pentadecylphenoxy)-hexanamido, alpha-(4-hydroxy-3-t-but-
ylphenoxy)-tetradecanamido, 2-oxo-pyrrolidin-1-yl,
2-oxo-5-tetradecylpyrro- lin-1-yl, N-methyltetradecanamido,
N-succinimido, N-phthalimido, 2,5-dioxo-1-oxazolidinyl,
3-dodecyl-2,5-dioxo-1-imidazolyl, and N-acetyl-N-dodecylamino,
ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino,
hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino,
phenylcarbonylamino, 2,5-(di-t-pentylphenyl)carbonylamino,
p-dodecylphenylcarbonylamino, p-tolylcarbonylamino, N-methylureido,
N,N-dimethylureido, N-methyl-N-dodecylureido, N-hexadecylureido,
N,N-dioctadecylureido, N,N-dioctyl-N'-ethylureido, N-phenylureido,
N,N-diphenylureido, N-phenyl-N-p-tolylureido,
N-(m-hexadecylphenyl)ureido,
N,N-(2,5-di-t-pentylphenyl)-N'-ethylureido, and t-butylcarbonamido;
sulfonamido, such as methylsulfonamido, benzenesulfonamido,
p-tolylsulfonamido, p-dodecylbenzenesulfonamido,
N-methyltetradecylsulfon- amido, N,N-dipropylsulfamoylamino, and
hexadecylsulfonamido; sulfamoyl, such as N-methylsulfamoyl,
N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-hexadecylsulfamoyl,
N,N-dimethylsulfamoyl, N-[3-(dodecyloxy)propyl]sulf- amoyl,
N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamoyl,
N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; carbamoyl,
such as N-methylcarbamoyl, N,N-dibutylcarbamoyl,
N-octadecylcarbamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl,
N-methyl-N-tetradecylcarbam- oyl, and N,N-dioctylcarbamoyl; acyl,
such as acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl,
p-dodecyloxyphenoxycarbony- l methoxycarbonyl, butoxycarbonyl,
tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl,
3-pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such as
methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl,
2-ethylhexyloxysulfonyl, phenoxysulfonyl,
2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl,
2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl,
phenylsulfonyl, 4-nonylphenylsulfonyl, andp-tolylsulfonyl;
sulfonyloxy, such as dodecylsulfonyloxy, and hexadecylsulfonyloxy;
sulfinyl, such as methylsulfinyl, octylsulfinyl,
2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl,
phenylsulfinyl, 4-nonylphenylsulfinyl, and p-tolylsulfinyl; thio,
such as ethylthio, octylthio, benzylthio, tetradecylthio,
2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio,
2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such as
acetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy,
N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and
cyclohexylcarbonyloxy; amine, such as phenylanilino,
2-chloroanilino, diethylamine, dodecylamine; imino, such as 1
(N-phenylimido)ethyl, N-succinimido or 3-benzylhydantoinyl;
phosphate, such as dimethylphosphate and ethylbutylphosphate;
phosphite, such as diethyl and dihexylphosphite; a heterocyclic
group, a heterocyclic oxy group or a heterocyclic thio group, each
of which may be substituted and which contain a 3 to 7 membered
heterocyclic ring composed of carbon atoms and at least one hetero
atom selected from the group consisting of oxygen, nitrogen,
sulfur, phosphorous, or boron, such as 2-furyl, 2-thienyl,
2-benzimidazolyloxy or 2-benzothiazolyl; quaternary ammonium, such
as triethylammonium; quaternary phosphonium, such as
triphenylphosphonium; and silyloxy, such as trimethylsilyloxy.
[0023] If desired, the substituents may themselves be further
substituted one or more times with the described substituent
groups. The particular substituents used may be selected by those
skilled in the art to attain the desired desirable properties for a
specific application and can include, for example,
electron-withdrawing groups, electron-donating groups, and steric
groups. When a molecule may have two or more substituents, the
substituents may be joined together to form a ring such as a fused
ring unless otherwise provided. Generally, the above groups and
substituents thereof may include those having up to 48 carbon
atoms, typically 1 to 36 carbon atoms and usually less than 24
carbon atoms, but greater numbers are possible depending on the
particular substituents selected.
EXAMPLES
Example 1
[0024] 2L 4-necked flask equipped with sealed mechanical stirrer,
thermometer, and reflux condenser, dropping funnel and nitrogen
inlet was charged with compound 7 (130.00 g, 256 mmol) and dry
propionitrile (1000 ml). BF.sub.3Et.sub.2O (156 ml, 1250 mmol) was
added from the funnel, after 1 hour the reaction mixture was warmed
about 97.degree. C. and refluxed for 36 hours. Before the reaction
mixture was cooled to RT about half of propionitrile was removed by
fast distillation. The cool concentrated reaction mixture was
slowly (over 20-30 minutes) added to water (10L) at 18-28.degree.
C. The water mixture was stirred (1-3 h) to solidified product
which was isolated by filtration, washed with water (400 ml),
saturated sodium bicarbonate (400 ml), water (3.times.400 ml) and
dried with flow of air for 3 hours. The crude product was
transferred to flask, slurry with i-Pr.sub.2O (600 mL), stirred for
0.5 h, filtered off, washed with Et.sub.2O (250 mL) and dried with
flow of air for 1-2 h and then in vacuum oven at 70.degree. C. for
6-12 hours to yield 119.6 g (83%) of the desire product--Inv 7.
Examples 2, 3
[0025] These were synthesized in the same manner as Example 1
except solvent and temperature selection as indicated in the
table.
Examples 4-6
[0026] The protonated starting compound 7 (1.30 g, 2.56 mmol), 10
ml of an appropriate dry solvent (tetrahydrofuran, toluene or
dichloromethane) and BF.sub.3Et.sub.2O (1.56 ml, 12.50 mmol) were
combined in a sealed bottle and heated at the temperature indicated
in the Table 1.
[0027] The progress of the reactions was monitored by TLC and LC
analysis.
[0028] Table 1 summarizes the examples including the reaction
conditions applied in the synthesis of bis(azinyl)amine-BF.sub.2
complex from deprotonated bis(azinyl)amine compound in different
solvents and resulting yields. The yields are based on protonated
compound starting material.
1TABLE 1 Illustrative Examples for Making, Inv-7 (36 hrs) Example
Type Solvent Temp. Yield 1 Inventive propionitrile 97.degree. C.
83% 2 Inventive acetonitrile 80.degree. C. 79% 3 Inventive
butyronitrile 115.degree. C. 91% 4 Comparative toluene 115.degree.
C. 4% 5 Comparative tetrahydrofuran 65.degree. C. <1% 6
Comparative dichloroethane 65.degree. C. <1%
[0029] Table 1 shows that, for the samples tested, the yields using
innovative process range from 70-91% yield, while those for the
comparative process ranged from 0-4%. Poor results with bulky
substituents wee also observed with solvents such as DMSO and
DMF.
[0030] The entire contents of the patents and other publications
referred to in this specification are incorporated herein by
reference.
* * * * *